Alkylolamino-methylene compound and method of making



,Pa tentecl Aug. 15, 1939 UNITED STATES ALKYLOLAIWINO-METHYLENE COMPOUND AND METHOD OF MAKING Jean G..Kern, East Aurora, N. Y., assignor to National Aniline and Chemical Company, Inc.,

New York, N. Y., a corporation of New York No Drawing. Application August 11, 1936, Serial No. 95,481-

19 Claims.

This application relates to a new class of chemical compounds and to the production and use of such compounds. It is in part a continuation of my application Serial No. 691,819,

filed October 2, 1933.

The present invention comprehends a new class of chemical compounds,the alkylolaminomethylene sulfurous acids, sulfites, and sulfoxylates of the following general formula:

:5 .metal atoms; a: is aninteger which equals the valence of Am, and z is an integer less than 3.

Compounds of the present invention may be prepared from primary -or secondary alkylolamines by reaction thereof with a hydroxymethylene sulfite or sulfoxylate derived from an aldehyde or a ketone.

When derived from an aldehyde the compounds of the present invention may be represented by the formula:

wherein R1 represents a member of the group consisting of alkylene, cycloalkylene, hydroxyalkylene, and polyhydroxy-alkylene radicals; R2 represents a member of the group consisting of hydrogen, alkyl and cycloalkyl radicals, and the radical HO-R1; R3 represents a member of the group consisting of hydrogen and alkyl and aryl radicals; Am represents a member of the group consisting of hydrogen and metal atoms; a: represents an integer equal to the valence of Am, and z is an integer less than 3. When derived from a ketone the compounds of the present invention may be represented by the formula:

wherein;R1 represents a member of the group consisting of alkylene, cycloalkylene, hydroxy- Y alkylene', and polyhydroxy-alkylene radicals; R2 represents a member of the group consisting of hydrogen, alkyl and cycloalkyl radicals, and the radical HO-Ru R3 represents an alkyl group; R4 represents an alkyl group; Am represents a member of the group consisting of hydrogen and metal atoms; :0 represents an integer equal to the valence of Am; and z'is an integer less than 3. The compounds of the present invention are useful as bactericides, insecticides, and germicides. Suchcompounds wherein Am represents a copper or mercury atom are in particular notable for their parasiticidal activity.

The alkylolamino-methylene sulfites of the present invention are particularly suitable for use as intermediates in the preparation of many valuable compounds, for instance they may be employed for the preparation of alkylolaminomethylene nitriles, alkylolamino-methylene esters of diazo-sulfonic acids, alkylolaminmdiazo compounds, and alkylolamino-sulfoxylates. The alkylolamino-sulfoxylates in turn, as well as the sulfites themselves, are valuable dye assistants.

The general reaction by which the compounds of the present invention may be prepared from aldehyde or ketone, hydrogenor metal sulfites and alkylolor cyclo-alkylolamines is illustrated by the following equation applicable to the bisulfites and monovalent metal sulfites:

wherein R1; R2, R3, and R4 have the values assigned in Formula 1, and Am represents hydrogen or a monovalent metal. The reaction takes place readily at normal temperatures, usually with the evolution of heat. The rate of reactionordinarily may be increased by raising the temperature to 50 C. to 70 C.

In the following examples the quantities are expressed as parts by weight.

EXAMPLE 1.Mono-ethanolamino-mthylevze sulfite of sodium ethanolamine, HO-CH2CH2NH2 are added vigorously, and its temperature is allowed to rise to about 70' C. After about one hour of agitation 'at this temperature the reaction is substantially complete.

The resulting solution may be used directly, or,

if a dry product is desired, the solution may be evaporated to dryness in vacuo. The product thus obtained has the following probable formula:

it is exposed to the atmosphere, especially one" that is warm and moist, it decomposes slowly. When heated in aqueous solutions of alkalis or acids (organic or mineral), this product splits up into its original components-that is,'ethanolamine, formaldehyde, and sulfur dioxide. This reaction. tends to conflm the constitution w signed thereto in the formula above. The product also forms earth-alkali-metal salts, and heavy metal salts; among the latter the copper and mercury salts are of particular value as bactericides. Thesodium salt of the product is an excellent bactericide, germicide and insecticide. When they are treated. with potassium cyanide or sodium cyanide, the hydroxy-alkylaminomethylene suliltes react to form nitriles (Knoevenagel, Ber. 3'7, 4075; Ber. 37, 4080; Her. 38. 218) which, upon saponiflcation, yield alpln-alkylolamino-acids. Thus ethanolamino-methylene potassium sulfite forms ethanolamino-methylene-nitrile, according to the equation an no cm-cm-mr cm-o-solx+xcu KcSOa-i-HO-CHe-CHr-NHM and this compound hydrolyzes readily to yield ethanolamino-acetlc acid, according to the equation:

(7) HOCHzCH:- -NH-CHa-CN+2H:O-

HOCHaCIh-NI -I.-CH:COOH+NH:

The hydroxy-alkylaminn-methylene sulfltes are readilyreduced with Zn dust and acetic acid,

and yield the corresponding formaldehyde sul-- fomlates; thus ethanolamino methylene potasslum sulflte yields ethanolamino-formaldehydesulfoxylate, according to the equation:

Example 2.-Diethanolamno-methfll ne-sulfltc 'of sodium To the mono-molar solution of formaldehydebisulflte prepared as in Example 1, 105 parts of diethanolamine (1 mol) are added while the temperature of the reactive mass is not allowed to rise above about 75 C. The mixture is maintained between 70 C. and 75 C., for one to two hours, or until reaction is substantially complete. The solution thus obtained may be used directly, or if a dry product is desired, it is distilled in vacuo until suflicient excess wateris removed to sueavae cause the diethanolamlno-methylene-sulflte of sodium to crystallize from the solution. The product has the probable formula:

It is a very stable compound in dry form or in aqueous solution. When treated with cold or hot caustic alkalis or acids, it is decomposed into diethanolamine, formaldehyde, and sulfur dioxide. Its properties are for the most part similar to those of the product obtained in Example 1; but

[it has the properties of a tertiary amine, and is diflerentiated thereby from the product of Example 1.

When diethanolamino-methylene-bisulflte or the sodium salt thereof is submitted to reduction, for instance with Zn dust and glacial acetic acid, a body is formed which, as in Example 1, contains one oxygen atom less than the parent body; it is the corresponding diethanolamino-formaldehyde-sulfoxylate. This reducing reaction may be written as follows: I

Exam: 3.Mono-ethanolamino-ethylidene, po-

. tassiurn-sulflte 44 parts of' acetaldehyde, CHa-CHO, (substantially free from polymerization products such as metaldehyde or paraldehyde) are added slowly to a vigorously agitated solution of 120 parts of potassium bisulilte dissolved in as little water. as possible. The following reaction takes place:

cmcno+no-a 0.x no-cn-o s on:

As soon as the temperature of the reaction mixture ceases to rise, 61 parts of mono-ethanolamine are added to the mass which is then maintained from 1 to 2 hours at about 70 C.

The solution is then heated in vacuo to remove water, and leaves a white crystalline residue of mono-ethanolamino-ethylidene potassium sulflte. Its probable formula'is:

no-cmcm-me-cn-o 5 one This product is similar in its properties to the products obtained according to the preceding examples, and undergoes the same reactions.

ample 1, an equimolecular quantity of N-methylethanolamine, QHsNHCsHeQH, is substituted for the mono-ethanolamine. The resulting product has the. following probable formula:

EXAMPLE 5.Monoethanolamino-isopropylidenesodium sulfite 58 parts of acetone, 104 parts of sodium bisulfite and to parts water are mixed very slowly until the reaction mass begins to cool down again. The reaction is preferably carried out in a vessel fitted with a reflux condenser. To the resulting mixture 61 parts of mono-ethanolamine are added and the solution is kept for two hours at a temperature of about 70 C. The reaction mixture is allowed to stand (about 16 hours) until the product crystallizes therefrom. The crystalline product is separated by filtration and dried. It formula is probably on. HO(H CHzNH-( 3O s OzNa 14 $11. EXAMPLE 6.-Diethanolamino-isopropylidene-sodiam sulfite As in Example 5, a mixture of 58 parts of acetone and 104 parts of sodium bisulfite are reacted by adding thereto 50 parts of water, and after the first condensation is finished, 105 parts of diethanolamine are added to the mixture. The product which finally crystallizes from the reaction mixture in the form of beautiful white crystals. has the following probable formula:

finished 91 parts of amino-propanediol are added to the reaction mass which is then heated for about two hours at a temperature between 70 C. and 75 C. From the cooled reaction mixture a white crystalline product of excellent solubility is obtained. It is mono-propanediolamino-benzal-sodium sulfite which is probably represente by the formula,--

EXAMPLE 8. parts benzaldehyde-ortho-sulfonic acid are dissolved in 1000 parts water with enough soda ash to just bring the product into solution. 104 parts sodium-bisulfite are added slowly; the temperature of the mixture rises to about 50 C. and is kept between about 50 C. and about 60 C. for about one-half ,hour. Now 105 parts diethanolamine are added slowly; the temperature of the mass rises to between 75 C. and 80 C. during the addition. The reaction mixture is kept between about 70 C. and about 75 C. for about two hours to complete the reaction. The product need not be isolated but may be used as a solution. The solution prepared as above will contain about 414 parts of the new compound having the following probable formula:

' 7 011-0 s OzNa taiiary Hydroxyanothylene Tertiary butanolamino methylene bntanol sulfite oi Na sulilte oi Na CH] CH;

N-cydobexyl-ethanolamine Hydroxy-methylene N-cycloheryl-otbanolamino methylene sulflte ol'N suliite of Na HOCIhCH;

oa. 011, oHl om CHr-CHa sax-om Momethanolamine Hydroxy-bonzal-suflte oisodium The sthanolamlno-benzalo suliite oi sodium I /O.S:Na

NKrCH;-CH:0H+HO-CHO.SO,Na CH\ (26) NH-ClirCHr-OH N-cycbheryl- Hydroxy-2,5-disullo- N-cycloheryl-ethanolamino-z, othanolamim bonzal-sulfite oi -disuiio-benzal-sulfite of sodium sodium CHr-CHrOH HO-CH-O.SO2N8 /O.SO:NB (27) N car-cm on CHT-CHlOH SOaNa cn oH, I N\ /CHr-CH1\ era-0H. N801 CH\ en",

- CHr-CHs SOIN! SOxNB die compositions which also contain dyeing and printing assistants.

Exunn 9.--A vat obtained as follows:

100 parts of Carbanthrene Blue GCD, Color "Index No. 1113, and containing 16.5 per cent dry color solids, and 1 per cent Leukanol are mixed with 82.5 parts of the sodium salt of diethanolamino-methylene-suliurous acidand evaporated until the mixture attains the consistency of a heavy paste. The paste is then transferred to a dry ng pan and evaporated in vacuo at a temperature of about 60 C. The dried mass is ground to a fine powder and screened. The Carhanthrene Blue powder thus obtained is readily dispersible, can be used for printing and dyeing, and yields shades of great brillianoy with excellent penetration. It has working properties which are superior to those of ordinary Carbanthrene Blue GCD paste, and it yields for an color preparation may be equal weight of dye solids, stronger prints than,

the Carbanthrene Blue GCD from which it is made.

It is to be understood that the above vat dye preparation may comprise also other assistants, in particular the soluble partial ester salts of inorganic oxy-acids with monoor polyhydroxy organic compounds, such as are disclosed in applications Serial Nos. 673,030 and 673,031, filed May 28, 1933. Thus, a vat powder of the following composition Parts Dry Blue GOD, Color Index No. 1113 16.5 Dry Leuka'nol 1(2) Sodium isobutyl sulfate Dlethanolamino-methylene-sodium sulflte 71.5

is a product which disperses very readily in either water or printing paste.

Similar results are obtainable if in Example 9 any of the.vat dyes mentioned in applications Serial Nos. 673,030 and 673,031 are substituted for the Carbanthrene Blue GCD. Similarly, the stated amino-methylene-sulfites may be replaced by any one or a mixture of hydroxyor poly-hydroxy-alkylamino-methylene sulfites hereinbefore defined.

The paste or powder vat dyestuii' preparations thus obtained may also contain any of the known assistants and catalysts as disclosed in the prior art, such as alkyl partial ester sulfates or phosphates, anthraquinone derivatives, alkylolemines, hydroxy-alkyl ethers, etc.

ExAnPLr: 10,-100 parts of a press cake composed oi 30 parts dry Carbanthrene Violet 2R, Color Index No. 1104, and '70 parts water are thinned with 6 parts Leukanol. To this mixture 85 parts of diethanolamine are added; the paste is stirred until it is homogeneous, then 109 parts anhydrous sodium formaldehyde bisulfite are added thereto, and the mixture is agitated and heated to about 70 0., until the bisulflte is completely dissolved, and the reaction is complete, i. e. from about 1% hours to about 2 hours. Upon cooling the resulting mass a solid agglomeration is obtained which may be ground to a fine powder alkali-metal salts.

in vacuo. The final dry product is a very intimate mixture of thedispersed vat dye, Leukanol, and diethanolamino-methylene-sulfoxylate of sodium. This vat dye preparation in the form of paste or powder has an advantage in dyeing and printingcompositions' and processes over other vat dye compositions since it contains both an assistant and a reducing agent in a combined form. Furthermore, the preparations of this,

type possess a highdegree of uniformity since the amount of actual vat dye solids, and the amount of contained assistant-reductor are easily regulated, in the manufacture of the dye, to a very definite ratio, e. g., 10 parts dye for 50 parts assistant-reductor or more. The products can be dissolved, e. g., in an alkali-metal carbonate thickener, containing or not containing very small amounts of sodium formaldehyde sulfoxylate.

In the above examples Leukanol may be used in' wherein R1 represents a-member of the group consisting of alkylene, cycloallwlene, hydroxyalkylene, and polyhydroxy-alkylene radicals; R2 represents a member of the group consisting of hydrogen, alkyl and cycloalkyl radicals, and the radical HO-Rr; R3 represents a member of the group consisting of hydrogen and alkyl radicals; R4 represents a member of the group consisting of hydrogen and alkyl radicals and, only when R3 represents H, aryl radicals; Am represents a member of the group consisting of hydrogen and metal atoms; :c is' an integer which equals the valence of Am; and z is an integer less than 3.

2. A chemical compound of the group ethanolamino-methylene sulfurous acid and its alkalimetal salts. p

3. A chemical compound of the group diethanolamino-methylene sulfurous acid and its al-,

kali-metal salts.

4. A chemical compound of the group diethanolamino-isopropylidene' sulfurous acid andits 5. The process of making an alkylolaminomethylene sulfite compound, which comprises condensing a compound of the group consisting of aldehyde metal bisulfites and ketone metal bisulfites with an alkylolamine.

6. The process of making an alkylolaminomethylene sulflte compound, which comprises agitating a compound of the group consisting of aldehyde metal bisuliites and ketone metal bisul-" fites with an alkylolamine at a temperature be v tween 50 and 70 C.

7. A process for making an ethanolaminomethylene sulfite, which comprises heating ethanolamine with analkali-metal formaldehyde bisulflte.

8. A process for making a diethanolaminomethylene su'iflte, which comprises heating diethanolamine with an alkali-metal formaldehyde bisulflte.

9. A process for making a diethanolamino-isopropylidene sulflte, which comprises heating diethanolamine with an alkali-metal acetone bisulfite;

10. The process of making a compound of the general formula:

wherein R1 represents a member of thegroup consisting of alkylene, cycloalkylene, hydroxyalkylene, and polyhydroxy-alkylene radicals; R: represents a member of the group consisting of hydrogen, alkyl and cycloalkyl radicals, and the radical HO-R1; R3 represents a member of the with a compound ot the formula:

mama. 

